EP0964834B1 - Einführung von fluorid-ionen in glasteilchen - Google Patents

Einführung von fluorid-ionen in glasteilchen Download PDF

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Publication number
EP0964834B1
EP0964834B1 EP98907068A EP98907068A EP0964834B1 EP 0964834 B1 EP0964834 B1 EP 0964834B1 EP 98907068 A EP98907068 A EP 98907068A EP 98907068 A EP98907068 A EP 98907068A EP 0964834 B1 EP0964834 B1 EP 0964834B1
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EP
European Patent Office
Prior art keywords
glass
ammonium
fluoride
particles
cements
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98907068A
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English (en)
French (fr)
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EP0964834A1 (de
Inventor
Ademola Olaseni Akinmade
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
S&C POLYMER GmbH
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S & C Polymer GmbH
S& C Polymer GmbH
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Publication date
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Publication of EP0964834A1 publication Critical patent/EP0964834A1/de
Application granted granted Critical
Publication of EP0964834B1 publication Critical patent/EP0964834B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/77—Glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/836—Glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions

Definitions

  • This invention relates to a method of introducing fluoride ions into glass particles. Glass particles so treated may have a variety of uses.
  • glass particles may be used in making a particulate material by reacting them(if acid-degradable) to completion with an acid polymer, by an acid-base cement-forming reaction, and grinding the product.
  • Glass in this specification can include, according to the context, gelatinising minerals such as bentonite or other mixed metal oxides.
  • the resulting particulate material can be considered as a glass-depleted cement gel, and can be used in a number of distinct light cured dental materials, such as a liner, fissure sealant, bonding agent/adhesive and anterior restorative. It may also be incorporated in existing cement formulations as a fluoride releasing agent, e.g. incorporation in non-resin based cements and also existing resin based cements.
  • aluminosilicate glass is reacted with acid.
  • the outer layer of each glass particle is depleted of metal ions and is degraded to a silica gel.
  • the metal ions have been released by the action of the acid to migrate to the surrounding liquid phase, where they are initially soluble but then accumulate to cause gelation and become insoluble.
  • the resulting cement thus has the form of dispersed particles each having an unreacted aluminosilicate glass core surrounded by a metal-depleted silica gel shell, the shell being about 1 ⁇ 2 micron thick, the particles being dispersed in a gelated matrix of polyacid chains to which the metal ions which were released from the glass are bound.
  • the shell attained this thickness of about 1 ⁇ 2 micron during the period while the material surrounding it remained liquid and reactive. The shell ceases to thicken when the surrounding material has set.
  • the unreacted aluminosilicate glass cores would no longer remain.
  • the acid can release all the metal ions throughout the full depth of each particle before the system gels, leaving simply silica gel cores dispersed in a gelated matrix of polyacid chains to which the metal ions which were released from the glass are bound.
  • the more reactive the acid the larger the size of glass particle that can be wholly reacted, 1.2 - 1.4 ⁇ m being conceivable.
  • Such a hydrogel material is levigated for further use. Note that, all the glass having been leached by acid, no unwanted fresh unreacted glass surface can be exposed by such levigation or particularisation, and the hydrogel material is therefore inert in the presence of water and/or cement-forming acids.
  • An alternative use for glass treated according to the present invention is (when present in stoichiometric excess) as a component of a glass ionomer cement.
  • a method of introducing fluoride ions into glass particles not exceeding 2 micron comprises contacting the glass with a solution of an ammonium fluoride.
  • the solvent is added to the glass and fluoride.
  • the fluoride solution is one from which ammonia can evolve, such as ammonium hydrogen difluoride NH 4 .HF 2 , ammonium fluoride, ammonium heptafluorotantalate (V), ammonium hexafluorogermanate (IV), ammonium hexafluoroniobate, ammonium hexafluorophosphate, ammonium hexafluorosilicate, ammonium hexafluorotitanate (IV), ammonium tetrafluoroborate, ammonium trifluoroacetate or ammonium trifluoromethanesulfonate.
  • ammonium hydrogen difluoride NH 4 .HF 2 ammonium fluoride, ammonium heptafluorotantalate (V), ammonium hexafluorogermanate (IV), ammonium hexafluoroniobate, ammonium hexafluorophosphate, ammonium he
  • Bentonite for example, would not be reactive enough to participate in an acid-base reaction, but its reactivity can be improved by introducing fluoride as set forth above, typically by reacting the Al 2 O 3 to form AlF 3 .
  • the glass may be an aluminosilicate or otherwise acid-degradable.
  • ammonium salts is preferable to employing HF, to avoid risks.
  • the use of ammonium cations and fluoriferous anions will deposit F and no cations. Deposited cations will change the composition of the glasses, a complication avoided by the present invention.
  • ammonium hydrogen difluoride or its analogues deactivates the surfaces of glasses by the crystallisation of calcium fluoride.
  • glass ionomer cements glass polyalkenoate cements
  • this ammonium salt on fluoride-free glass can even result in fluoride-containing non-setting glasses, as well as snap setting glasses.
  • the former enables glass powders to be reacted with poly(acrylic acid) and tartaric acid in the presence of water to achieve neutralisation before gelation. Achieving neutralisation before gelation is a prerequisite to the formation of glass core-free cements.
  • the snap-setting glasses resulting in cements that can set rapidly at the ends of their working times, within 20 seconds, may be used in glass-ionomer cements, which could rival command cure resin-based cements in their rapidity of set and low oral solubility.
  • This method may be used on glass to be made into a particulate material as set forth above, whereby such material becomes suitable for use in a dental cement formulation as a fluoride release reservoir, and can be considered as a "reactive filler" compatible with most if not all dental material curing routes.
  • the invention makes possible single-paste resin systems, such as a light-curable paste comprising a cross-linkable monomer, a light-activated initiator and a particulate material as set forth above.
  • a light-curable paste comprising a cross-linkable monomer, a light-activated initiator and a particulate material as set forth above.
  • Such paste may further comprise a zinc-containing glass, a polyalkenoic acid and optionally water so packed as to keep the pH below 4, and optionally contains Ba, Sr or other divalent glass-forming radio-opaque cation from the reacted glass.
  • Another paste may further comprise an aqueous solution of an acid polymer capable of participating in a glass ionomer setting reaction.
  • These two pastes may be presented in a two-paste cement pack, packed out of contact with each other (and preferably in opaque and/or air-tight packaging as appropriate) until the time of use.
  • one or both pastes further comprise a non-zinc acid-degradable glass and/or a polymeric acid and/or water, such that neither paste reacts until it is unpacked and/or mixed with the other paste.
  • the glass is of particles of radius larger than the depth to which fluoride ions have been introduced when, with polyalkenoic acid and water and preferably without chelating agent, it can form a glass ionomer cement.
  • the glass to be fluoridated is added to the fluoride solution.
  • Example 1 was repeated, but using 2.158 g of ammonium hydrogen difluoride in step 1) instead of the 2.877 g.
  • the slurry was heat-treated for 24 hours at 220°C.
  • Example 1 was repeated, but using 1.439 g of ammonium hydrogen difluoride in step 1) instead of the 2.877 g.
  • Examples 1-3 as submicron glass is used, it (in particular the Ca ions in it) becomes fully fluoridated throughout, even if the order of addition of reagents is changed; thus the NH 4 .HF 2 may equally successfully be mixed dry with the glass, with the water stirred in afterwards. This latter order is preferred if the glass exceeds 1 micron and is intended for the use specified in Example 4. With that latter order of addition of reagents, the evolution of ammonia is noticeably steadier and slower.
  • Example 4 The following further steps were performed on the product of each of Examples 1-3:
  • Example 1 The amount of ammonium hydrogen difluoride used in Example 1 was selected to replace all the oxygen from the calcium oxide of the glass with fluoride ions.
  • the lesser amounts in Examples 2 and 3 were (obviously) meant to achieve less than total replacement.
  • the level of fluoride in the glass would have a bearing on the fluoride release from the resulting resin-modified cement, the reactivity of the glass in cement formation, and the strength of the resulting glass-ionomer cements. In these Examples, no temperature above 220C is required.
  • Example 1 were repeated using the stated order of addition of reagents NH 4 .HF 2 then water then glass. However in Example 5 the glass was of 5-micron spheres. There was the same immediate and strong evolution of ammonia as a vigorous surface reaction took place. The result was glass particles with an outer layer uniformly about 1 ⁇ 2 ⁇ m thick rich in crystalline CaF 2 and an inner unaffected core.
  • Z45 and Z72 two zinc-based glasses were fluorinated.
  • Z45 contains no fluoride while Z72 is a fluoride-containing glass. Both however yield glass ionomer cements which release no fluoride ions.
  • This Example is to create fluoride-releasing and workable "conventional" cements from the extremely fast-setting Z45 glasses, and to create releasable fluoride ions from the Z72 glasses and, by extension, light-cured cements deriving from them.
  • the compositions of Z45 and Z72 are described later.
  • the glasses were fluorinated using ammonium hydrogen difluoride thus:-
  • Z45/F/1.6 Six fluorinations of Z45 glass following the protocol outlined above were carried out, denoted Z45/F/1.6.
  • the Fluorination of Z45 Glass Constituents (weight, g) Experiment Z45 glass Water Ammonium salt Z45/F/1 50.00 50.00 2.842 Z45/F/2 50.00 50.00 2.842 Z45/F/3 50.00 50.00 2.000 Z45/F/4 50.00 50.00 3.500 Z45/F/5 50.00 50.00 2.300 Z45/F/6 50.00 50.00 2.540
  • the quantities of the ammonium salts used in the fluorination were informed by the quantity of calcium ions contained in the Z45 glass.
  • the composition of the Z45 glass is: Ingredients of Z45 Main Components Weight (g) Constituents Breakdown (g) CaO 9.24 10.01 ZaO 50.00 50.00 Bentonite EX048 30.50 - (silica) 22.59 (alumina) 5.07 (magnesia) 1.00 (potash) 0.41 (soda) 0.66 89.74 89.74
  • Z45 glass contain 0.1788 moles of Ca and O in the CaO.
  • 0.1788 moles of O is equivalent to 3.396g of F.
  • 3.396g of F is contained in 5.098g of ammonium hydrogen difluoride. This is equivalent to 2.842g of the ammonium salt and 50.00g of Z45 glass, the composition of Z45/F/1 and Z45/F/2.
  • Z45/F/3-6 contain less than the amount of F necessary for the stoichiometric conversion of all the O of CaO to F.
  • Z45/F/4 contains a large excess of F ions.
  • the composition of Z72 glass is: Ingredients of Z72 Constituents (weight, g) silica 20.10 alumina 5.30 lime 16.10 magnesia 1.54 soda 1.02 zinc oxide 47.50 fluoride 12.20
  • Z272 contains 16.10g (0.2875 moles) of lime, CaO. This is equivalent of 5.4625 g of F, and 8.1995 g of ammonium hydrogen difluoride. Therefore, 50.00g of Z72 requires 4.10g of the ammonium salt for the stoichiometric conversion of all its CaO into fluoride.
  • the Z45/F/x glasses were blended with dry poly(acrylic acid), PAA, and tartaric acid, TA, to form anhydrous cement powders. These were mixed with aqueous poly(acrylic acid) -based solution at powder:liquid ratios (p:1) of 3.6:1 to form cements. The resulting cements are equivalent to mixing 2 parts of Z45/F/x with 1 part of aqueous solution of 50 wt% PAA; and 10wt% TA.
  • Constituents of Cement Weight of Powder Constituents (g) Liquid Z45/F/X 6.25 - PAA 1.062 2.00 TA 0.062 1.00 Water - 5.00
  • the working and setting times of the Z45/F/X cements were Cement made from: Ammonium Salt Qty Used (g/50g) Working Time (min) Setting Time (mins) Z45 nil ⁇ 1 ⁇ 1.5 Z45/F/3 2.00 1.5 2.0 Z45/F/5 2.30 1.7 2.5 Z45/F/6 2.54 1.9 2.8 Z45/F/1&2 2.84 2.3 3.3 Z45/F/4 3.50 2.5 4.0
  • Ammonium hydrogen difluoride is seen to increase the working and setting times of cements and create practical cements from the fast-setting Z45 glass.
  • the progressive incorporation of F into the glass network is attended by an increase in working time of the resulting cements, probably by the increasing acidifying (decreasing basicity) action of F ions in the glass.
  • the determined fluoride (F) in the glass has been obtained using x-ray fluorescence
  • the ratio of theoretical/determined F shows that the efficacy of the F treatment decreases with increasing F agent used (theoretical F in glass).
  • the fluoride release was:- Cement Age Fluoride Released From Z45/F/X/n Cements Z45/F/3 cumulative F (% of F) Z45/F/2 cumulative F (% of F) Z45/F/4 cumulative F (% of F) 1 hour 0.5 0.7 0.3 2 hours 0.8 1.4 0.6 3 hours 1.1 2.2 0.9 4 hours 1.3 2.8 1.1 5 hours 1.4 3.4 1.3 6 hours 1.5 3.8 1.6 24 hours 3.0 7.5 3.4 5 days 5.0 14.4 5.8 8 days 6.4 17.6 8.1 14 days 8.1 21.7 10.5 1 month 8.7 27.8 15.6 2 months 13.7 41.5 23.4 3 months 16.6 54.4 29.2 4 months 19.1 66.0 34.3 Note that the fluoride released from the cements did not follow the trend of fluoride content of the cement's constituent glass. However, and more importantly, the levels of fluoride release from the cements is of the oder of magnitude exhibited by commercial polyalkenoate cements. Therefore, as with those cements, the cements in this Example
  • Glass Z72 (which already contains fluoride, which however does not leach out) was fluorinated as described.
  • the fluorinated glass (“Z72/F”) was used to make resin-modified cements being hybrids of dental resin composites and conventional glass-ionomer cements, cured for 4x20s using blue light (flexural specimens), or prepared in 2mm layers with 40s light curing/layer (compressive specimens).

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Claims (15)

  1. Verfahren zum Einführen von Fluoridionen in Glaspartikel, welche eine Größe von 2 um nicht übersteigen,
    gekennzeichnet durch,
    Kontaktieren des Glases mit einer Lösung aus einer Ammoniumfluorid-Lösung.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Ammoniumfluorid Ammoniumwasserstoffdifluorid NH4.HF2, Ammoniumfluorid, Ammoniumheptafluortantalat (V), Ammoniumhexafluorgermanat (IV), Ammoniumhexafluomiobat, Ammoniumhexafluorphosphat, Ammoniumhexafluorsilikat, Ammoniumhexafluortitanat (IV), Ammoniumtetrafluorborat, Ammoniumtrifluoracetat oder Ammoniumtrifluormethansulfonat ist.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Glas ein säureabbaubares Glas ist.
  4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Glas ein Aluminosilikatglas ist.
  5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Partikel eine Größe von 1½ µm nicht übersteigen.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Partikel eine Größe von 1 µm nicht übersteigen.
  7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Lösungsmittel den Glaspartikeln und dem Fluorid zugegeben wird.
  8. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Glaspartikel der Fluoridlösung zugegeben werden.
  9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß Fluoridionen über die gesamte Dicke der Glaspartikel eingeführt wurden.
  10. Glaspartikel, in die Fluoridionen mittels einem Verfahren gemäß einem der vorhergehenden Ansprüche zugeführt wurden.
  11. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß das Glas Partikel mit einem Radius umfaßt, welcher größer ist als die Tiefe, in die Fluoridionen eingeführt wurden.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Glaspartikel der Fluoridlösung zugegeben werden.
  13. Glaspartikel, in die Fluoridionen mittels einem Verfahren gemäß Anspruch 11 oder 12 zugeführt wurden.
  14. Glasionomerzement umfassend ein Glas gemäß Anspruch 13, eine Polyalkenoidsäure oder einen Vorläufer dieser und Wasser.
  15. Glasionomerzement nach Anspruch 14 ohne Chelatbildungsmittel.
EP98907068A 1997-03-03 1998-02-26 Einführung von fluorid-ionen in glasteilchen Expired - Lifetime EP0964834B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9704104A GB2322855A (en) 1997-03-03 1997-03-03 Introducing fluoride ions into glass
GB9704104 1997-03-03
PCT/GB1998/000607 WO1998039263A1 (en) 1997-03-03 1998-02-26 Introducing fluoride ions into glass particles

Publications (2)

Publication Number Publication Date
EP0964834A1 EP0964834A1 (de) 1999-12-22
EP0964834B1 true EP0964834B1 (de) 2003-07-23

Family

ID=10808424

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98907068A Expired - Lifetime EP0964834B1 (de) 1997-03-03 1998-02-26 Einführung von fluorid-ionen in glasteilchen

Country Status (5)

Country Link
EP (1) EP0964834B1 (de)
JP (1) JP2001513743A (de)
DE (1) DE69816596T2 (de)
GB (1) GB2322855A (de)
WO (1) WO1998039263A1 (de)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1119784A (en) * 1965-10-26 1968-07-10 Brockway Glass Co Inc Process for treating glass surfaces
NL6708670A (de) * 1967-06-21 1968-12-23
FR1563858A (de) * 1968-02-02 1969-04-18
CA1092358A (en) * 1977-08-18 1980-12-30 Leon Levene Method of strengthening glass articles with potassium fluoride-metal acetate
JPS5938926B2 (ja) * 1980-06-04 1984-09-20 而至歯科工業株式会社 フルオロ錯塩を含む歯科用グラスアイオノマ−セメント硬化液
JPS6267008A (ja) * 1985-09-20 1987-03-26 G C Dental Ind Corp 歯科用グラスアイオノマ−セメント用フルオロアルミノシリケ−トガラス粉末
JPH0755882B2 (ja) * 1987-02-13 1995-06-14 而至歯科工業株式会社 歯科用グラスアイオノマーセメント用ガラス粉末

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kirk-Othmer, Encyclopedia of Chemical Technology, 1994, Fourth Ed., Vol. 11, pp 287-289 *

Also Published As

Publication number Publication date
GB2322855A (en) 1998-09-09
GB9704104D0 (en) 1997-04-16
DE69816596T2 (de) 2004-04-15
EP0964834A1 (de) 1999-12-22
WO1998039263A1 (en) 1998-09-11
DE69816596D1 (de) 2003-08-28
JP2001513743A (ja) 2001-09-04

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